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UNIVERSITY OF CAMBRIDGE INTERNATIONAL EXAMINATIONS
General Certificate of Education Advanced Level
*4308885825*
9701/42
CHEMISTRY
Paper 4 Structured Questions
May/June 2010
1 hour 45 minutes
Candidates answer on the Question Paper.
Additional Materials:
Data Booklet
READ THESE INSTRUCTIONS FIRST
Write your Centre number, candidate number and name on all the work you hand in.
Write in dark blue or black pen.
You may use a pencil for any diagrams, graphs or rough working.
Do not use staples, paper clips, highlighters, glue or correction fluid.
DO NOT WRITE IN ANY BARCODES.
Section A
Answer all questions.
For Examiner’s Use
Section B
Answer all questions.
1
You may lose marks if you do not show your working or if you do not use
appropriate units.
A Data Booklet is provided.
At the end of the examination, fasten all your work securely together.
The number of marks is given in brackets [ ] at the end of each question or part
question.
2
3
4
5
6
7
8
Total
This document consists of 17 printed pages and 3 blank pages.
DC (SM/CGW) 22690/3
© UCLES 2010
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2
Section A
For
Examiner’s
Use
Answer all questions in the spaces provided.
1
Phenacyl chloride has been used as a component of some tear gases. Its lachrymatory and
irritant properties are due to it reacting with water inside body tissues to produce hydrochloric
acid.
It undergoes a nucleophilic substitution reaction with NaOH(aq).
O
Cl
+ OH–
+
phenacyl chloride
(a) Write the formulae of the products of this reaction in the two boxes above.
[2]
When the rate of this reaction was measured at various concentrations of the two reagents,
the following results were obtained.
experiment number
[phenacyl chloride]
[NaOH]
relative rate
1
0.020
0.10
1.0
2
0.030
0.10
1.5
3
0.025
0.20
2.5
(b) (i)
What is meant by the term order of reaction?
..................................................................................................................................
(ii)
Use the above data to deduce the order with respect to each reactant. Explain your
reasoning.
..................................................................................................................................
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..................................................................................................................................
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(iii)
Write the overall rate equation for the reaction.
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(iv)
Describe the mechanism for this reaction that is consistent with your overall rate
equation.
You should show all intermediates and/or transition states and partial charges, and
you should represent the movements of electron pairs by curly arrows.
For
Examiner’s
Use
[7]
(c) (i)
Describe an experiment that would show that CH3COCl reacts with water at a
much faster rate than phenacyl chloride. Include the reagents you would use, and
the observations you would make with each chloride.
..................................................................................................................................
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(ii)
Suggest an explanation for this difference in reactivity.
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[4]
[Total: 13]
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2
(a) Describe and explain how the solubilities of the sulfates of the Group II elements vary
down the group.
..........................................................................................................................................
..........................................................................................................................................
..........................................................................................................................................
..........................................................................................................................................
..........................................................................................................................................
...................................................................................................................................... [3]
(b) The following table lists some enthalpy changes for magnesium and strontium
compounds.
enthalpy change
value for magnesium
/ kJ mol–1
value for strontium
/ kJ mol–1
lattice enthalpy of M (OH)2
–2993
–2467
enthalpy change of hydration of M 2+(g)
–1890
–1414
enthalpy change of hydration of OH–(g)
–550
–550
(i)
o
for Mg(OH)2 and for Sr(OH)2.
Use the above data to calculate values of ΔH solution
Mg(OH)2 ...................................................................................................................
..................................................................................................................................
o
= ..................................... kJ mol–1
ΔH solution
Sr(OH)2 ....................................................................................................................
..................................................................................................................................
o
= ..................................... kJ mol–1
ΔH solution
(ii)
Use your results in (i) to suggest whether Sr(OH)2 is more or less soluble in water
than is Mg(OH)2. State any assumptions you make.
..................................................................................................................................
..................................................................................................................................
(iii)
Suggest whether Sr(OH)2 would be more or less soluble in hot water than in cold.
Explain your reasoning.
..................................................................................................................................
..................................................................................................................................
[5]
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5
(c) Calcium hydroxide, Ca(OH)2, is slightly soluble in water.
(i)
Write an expression for Ksp for calcium hydroxide, and state its units.
Ksp =
(ii)
For
Examiner’s
Use
units ............................................
25.0 cm3 of a saturated solution of Ca(OH)2 required 21.0 cm3 of 0.0500 mol dm–3
HCl for complete neutralisation.
Calculate the [OH–(aq)] and the [Ca2+(aq)] in the saturated solution, and hence
calculate a value for Ksp.
[OH–(aq)] = .................................
[Ca2+(aq)] = ................................
Ksp = .........................................................................................
(iii)
How would the solubility of Ca(OH)2 in 0.1 mol dm–3 NaOH compare with that in
water?
Explain your answer.
..................................................................................................................................
..................................................................................................................................
[6]
[Total: 14]
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3
(a) Fluorine is much more electronegative than both silicon and sulfur, but whereas the
molecule of SF4 has an overall dipole, that of SiF4 has none.
Suggest a reason for this difference.
..........................................................................................................................................
...................................................................................................................................... [1]
(b) Predict whether or not the following molecules will have an overall dipole. Place a tick in
the appropriate column.
compound
molecule has an
overall dipole
molecule does not have
an overall dipole
BCl 3
PCl 3
CCl 4
SF6
[2]
(c) Boron and silicon are two elements adjacent to carbon in the periodic table. CCl4 does
not react with water, whereas BCl 3 and SiCl4 do react.
(i)
Suggest a reason for this difference in reactivity.
..................................................................................................................................
..................................................................................................................................
(ii)
Construct equations showing the reaction of these two chlorides with an excess of
water.
BCl 3 .........................................................................................................................
SiCl4 .........................................................................................................................
[3]
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7
(d) When reacted with a small quantity of water, SiCl 4 produces an oxychloride X, SixCl yOz.
The mass spectrum of X shows peaks at mass numbers of 133, 149, 247, 263 and 396.
(You should assume that the species responsible for all these peaks contain the 16O,
the 35Cl and the 28Si isotopes only.)
(i)
For
Examiner’s
Use
Use these data to deduce the molecular formula of X.
molecular formula .........................................
(ii)
Suggest the structures of the fragments responsible for the peaks at the following
mass numbers.
mass number
structure
133
247
263
(iii)
Hence suggest the displayed formula of X.
[5]
[Total: 11]
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4
(a) Complete the electronic structures of the Cr3+ and Mn2+ ions.
Cr3+
1s22s22p6 .............
Mn2+
1s22s22p6 .............
For
Examiner’s
Use
[2]
(b) (i)
Describe what observations you would make when dilute KMnO4(aq) is added
slowly and with shaking to an acidified solution of FeSO4(aq) until the KMnO4 is in
a large excess.
..................................................................................................................................
..................................................................................................................................
..................................................................................................................................
..................................................................................................................................
..................................................................................................................................
..................................................................................................................................
(ii)
Construct an ionic equation for the reaction that occurs.
..................................................................................................................................
[4]
(c) By selecting relevant E o data from the Data Booklet explain why acidified solutions of
Fe2+(aq) are relatively stable to oxidation by air, whereas a freshly prepared precipitate
of Fe(OH)2 is readily oxidised to Fe(OH)3 under alkaline conditions.
relevant E o values and half equations
..........................................................................................................................................
..........................................................................................................................................
..........................................................................................................................................
..........................................................................................................................................
explanation
..........................................................................................................................................
..........................................................................................................................................
[4]
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(d) Predict the organic products of the following reactions and draw their structures in the
boxes below. You may use structural or skeletal formulae as you wish.
For
Examiner’s
Use
hot conc.
MnO4– + H+
hot conc.
MnO4– + H+
hot
Cr2O72– + H+
OH
OH
[4]
(e) KMnO4 and K2Cr2O7 are the reagents that can be used to carry out the following
transformation.
I
II
CHO
OH
E
(i)
Draw the structure of intermediate E in the box above.
(ii)
Suggest reagents and conditions for the following.
reaction I ...................................................................................................................
reaction II ..................................................................................................................
[3]
[Total: 17]
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5
(a) (i)
Briefly explain why the benzene molecule is planar.
..................................................................................................................................
..................................................................................................................................
..................................................................................................................................
(ii)
Briefly explain why all the carbon-carbon bonds in benzene are the same length.
..................................................................................................................................
..................................................................................................................................
..................................................................................................................................
[2]
(b) Benzene can be nitrated by warming it with a mixture of concentrated sulfuric and
nitric acids.
(i)
By means of an equation, illustrate the initial role of the sulfuric acid in this
reaction.
..................................................................................................................................
(ii)
Name the type of reaction and describe the mechanism for the nitration reaction,
including curly arrows showing the movement of electrons and all charges.
type of reaction .........................................................................................................
mechanism
[4]
(c) State the reagents and conditions needed to convert benzene into chlorobenzene.
...................................................................................................................................... [1]
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11
(d) Nitrobenzene undergoes further substitution considerably more slowly than chlorobenzene.
In nitrobenzene the incoming group joins to the benzene ring in the 3-position, whereas
in chlorobenzene the incoming group joins to the benzene ring in the 4-position.
(i)
For
Examiner’s
Use
Use these ideas to suggest the structures of the intermediate compounds Y and Z
in the following synthesis of 4-chlorophenylamine.
NH2
I
II
III
Y
(ii)
Cl
Z
Suggest the reagents and conditions needed for reaction III in the above
synthesis.
..................................................................................................................................
..................................................................................................................................
(iii)
Suggest the structural formulae of the products A, B, C and D of the following
reactions. If no reaction occurs write “no reaction” in the relevant box.
NH2
CH3COCl
Br2(aq)
A
B
Cl
–
OH (aq)
C
NaNO2
+ HCl
D
[8]
[Total: 15]
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Section B
Answer all questions in the spaces provided.
6
Human hair and silk both consist of proteins. Proteins are described as having three major
levels of structure: primary, secondary and tertiary.
(a) Outline what is meant by the terms primary structure and tertiary structure of a protein.
primary structure ..............................................................................................................
..........................................................................................................................................
..........................................................................................................................................
tertiary structure ..............................................................................................................
..........................................................................................................................................
..........................................................................................................................................
[2]
(b) In hair, the secondary structure consists of α-helices which are cross-linked by
disulfide bonds. The amino acid responsible for this cross-linking is cysteine,
H2NCH(CH2SH)CO2H.
(i)
Show by means of a diagram how the disulfide cross-links are formed.
(ii)
What type of reaction is this?
..................................................................................................................................
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13
(iii)
State three other interactions that stabilise the tertiary structure of proteins.
..................................................................................................................................
For
Examiner’s
Use
..................................................................................................................................
..................................................................................................................................
[4]
(c) The β-pleated sheet is a different form of secondary structure found in proteins, such as
those in silk.
(i)
What type of bonding is responsible for stabilising the β-pleated sheet in silk?
..................................................................................................................................
(ii)
On the diagram below, draw a second polypeptide strand and show how bonds
would be formed that stabilise this β-pleated sheet.
R
H
O
R
H
O
CH
N
C
CH
N
C
N
C
CH
N
C
CH
H
O
R
H
O
R
[3]
(d) The cysteine-containing protein in hair is called α-keratin. A similar sequence of amino
acids can produce β-keratin proteins found in the scales, claws and shells of reptiles
such as tortoises. In β-keratin the secondary structure of the protein is in the form of a
β-pleated sheet.
Suggest what makes the β-pleated sheet in β-keratin so much less flexible than the
β-pleated sheet in silk.
..........................................................................................................................................
..........................................................................................................................................
...................................................................................................................................... [1]
[Total: 10]
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7
A mixture of amino acids may be separated using electrophoresis. A typical practical set-up
is shown in the diagram.
d.c. power supply
+
electrolyte
–
amino acid mixture placed here
glass slides
filter paper soaked in buffer solution
(a) When the power supply is switched on, some amino acids may not move, but remain
stationary. Suggest an explanation for this observation.
..........................................................................................................................................
..........................................................................................................................................
...................................................................................................................................... [2]
(b) The amino acid glycine has the formula H2NCH2CO2H. Identify the species formed on
the filter paper if glycine moves to the left (positive) end of the filter paper.
..................................................................
[1]
(c) The following result was obtained from another electrophoresis. What can be deduced
about the relative sizes of, and charges on, the amino acid species A, B and C?
+
–
A
B
C
mixture placed here
amino acid
relative size
charge
A
B
C
[3]
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15
(d) The sequence of amino acids in a polypeptide may be determined by partial hydrolysis
of the chain into smaller pieces, often tripeptides.
(i)
For
Examiner’s
Use
Following such a partial hydrolysis, the following tripeptides were obtained from a
given polypeptide.
ala-gly-asp
gly-ala-gly
lys-val-ser
ser-ala-gly
val-ser-ala
Given that the N-terminal amino acid is lysine (lys) suggest the amino acid sequence
of the shortest polypeptide that would give the above tripeptides.
..................................................................................................................................
The structural formulae of the amino acids in the polypeptide are given below.
(ii)
abbreviation
amino acid
structural formula
ala
alanine
asp
aspartic acid
gly
glycine
H2NCH2CO2H
lys
lysine
H2NCH(CH2CH2CH2CH2NH2)CO2H
ser
serine
H2NCH(CH2OH)CO2H
val
valine
H2NCH(CH(CH3)2)CO2H
H2NCH(CH3)CO2H
H2NCH(CH2CO2H)CO2H
Which of the tripeptides in (i) has the lowest Mr?
..........................................................................
(iii)
Select one amino acid from those listed in the table which contains an ionic
side-chain at pH 8.
..........................................................................
[4]
[Total: 10]
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8
The design and development of batteries has been a major research area in recent years.
(a) Lead-acid batteries, used in cars, are made up of a number of rechargeable cells in
series, and were first developed in 1860. They have the disadvantage of a relatively high
mass compared to the energy stored. During discharge, the electrode reactions in the
cells of these batteries are as follows.
I
Pb + SO42– J PbSO4 + 2e–
II
PbO2 + 4H+ + SO42– + 2e– J PbSO4 + 2H2O
State which of these reactions occurs at the positive electrode in a lead-acid cell during
discharge, explaining your answer.
..........................................................................................................................................
...................................................................................................................................... [1]
(b) Use the Data Booklet and the equations I and II above to calculate the voltage produced
by a lead-acid cell under standard conditions.
[2]
(c) Nickel-metal hydride batteries were developed in the 1980s and have become
increasingly common particularly for small devices such as mobile phones and digital
cameras that need near-constant sources of electrical energy. These cells use nickel
oxohydroxide (NiO(OH)) as one electrode and a hydrogen-absorbing alloy such as LiNi5
as the other electrode.
One reaction that takes place in these batteries is
NiO(OH) + H2O + e–
Ni(OH)2 + OH–
(i)
State the oxidation state of nickel in NiO(OH). .....................
(ii)
Suggest a likely advantage of these batteries compared with lead-acid batteries.
..................................................................................................................................
..................................................................................................................................
[2]
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Examiner’s
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17
(d) Hydrogen fuel cells have been suggested as the next major advance in electrically
powered vehicles. In these fuel cells hydrogen is oxidized to produce water, using a
catalyst and inert electrodes.
(i)
Suggest a material for the electrodes.
..........................................................................
(ii)
Use your knowledge of hydrogen to suggest a disadvantage of these fuel cells in
powering vehicles.
..................................................................................................................................
..................................................................................................................................
[2]
(e) Many of the world’s countries are developing ways of recycling materials which are
valuable or which require large amounts of energy to produce.
For each of the following recyclable materials, state whether recycling of this material is
important in saving energy or in saving resources. Use your knowledge of chemistry to
explain each choice.
glass ................................................................................................................................
..........................................................................................................................................
..........................................................................................................................................
steel .................................................................................................................................
..........................................................................................................................................
..........................................................................................................................................
plastics .............................................................................................................................
..........................................................................................................................................
..........................................................................................................................................
[3]
[Total: 10]
© UCLES 2010
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Examiner’s
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18
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University of Cambridge International Examinations is part of the Cambridge Assessment Group. Cambridge Assessment is the brand name of University of
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